Heat treatable coated article with diamond-like carbon (DLC) and/or zirconium in coating

ABSTRACT

In certain example embodiments, a coated article includes a zirconium nitride inclusive layer before heat treatment (HT). The coated article is heat treated sufficiently to cause the zirconium nitride based layer to transform into a zirconium oxide based layer that is scratch resistant and/or durable. In certain example embodiments, the zirconium nitride and/or zirconium oxide may be doped with F and/or C.

This application is a continuation-in-part (CIP) of U.S. patentapplication Ser. No. 10/994,207, filed Nov. 22, 2004, and a CIP of Ser.No. 10/785,707, filed Feb. 25, 2004, and also a CIP of 10/700,359, filedNov. 4, 2003, the entire disclosures of which are all herebyincorporated herein by reference.

This invention relates to a method of making a coated article to be usedin a window unit or any other suitable application such as furnitureglass or picture frame glass. For example, certain embodiments of thisinvention relate to a method of making a window unit (e.g., vehiclewindow such as vehicle windshield, backlite, sunroof, or sidelite, or IGwindow unit, or shower door window) including a step of heat treating aglass substrate coated with at least a layer comprising zirconiumnitride and/or diamond-like carbon (DLC). In certain exampleembodiments, the glass substrate may be coated with only a layer of orincluding zirconium nitride, and the be heat treated where the zirconiumnitride inclusive layer transforms into a layer comprising zirconiumoxide due to the heat treatment.

Optionally, DLC may be provided over the zirconium nitride prior to heattreatment. DLC may be used to generate energy during heat treatment (HT)for transforming at least another layer in the coating so as to form anew post-HT layer(s) which was not present before the heat treatment.

Certain other example embodiments of this invention relate to such acoated article, heat treated or not, which may be used in windowapplications, or any other suitable application such as furniture glassor the like.

BACKGROUND OF THE INVENTION

Vehicle windows (e.g., windshields, backlites, sunroofs, and sidelites)are known in the art. For purposes of example, vehicle windshieldstypically include a pair of bent glass substrates laminated together viaa polymer interlayer such as polyvinyl butyral (PVB). It is known thatone of the two glass substrates may have a coating (e.g., low-E coating)thereon for solar control purposes such as reflecting IR and/or UVradiation, so that the vehicle interior can be more comfortable incertain weather conditions. Conventional vehicle windshields are made asfollows. First and second flat glass substrates are provided, one ofthem optionally having a low-E coating sputtered thereon. The pair ofglass substrates are washed and booked together (i.e., stacked on oneanother), and then while booked are heat bent together into the desiredwindshield shape at a high temperature(s) (e.g., 8 minutes at about600-625 degrees C.). The two bent glass substrates are then laminatedtogether via the polymer interlayer to form the vehicle windshield.

Insulating glass (IG) window units are also known in the art.Conventional IG window units include at least first and second glasssubstrates (one of which may have a solar control coating on an interiorsurface thereof) that are coupled to one another via at least oneseal(s) or spacer(s). The resulting space or gap between the glasssubstrates may or may not be filled with gas and/or evacuated to a lowpressure in different instances. However, many IG units are required tobe tempered. Thermal tempering of the glass substrates for such IG unitstypically requires heating the glass substrates to temperature(s) of atleast about 600 degrees C. for a sufficient period of time to enablethermal tempering.

Other types of coated articles also require heat treatment (HT) (e.g.,tempering, heat bending, and/or heat strengthening) in certainapplications. For example and without limitation, glass shower doors,glass table tops, and the like require HT in certain instances.

Diamond-like carbon (DLC) is sometimes known for its scratch resistantproperties. For example, different types of DLC are discussed in thefollowing U.S. Pat. Nos. 6,303,226; 6,303,225; 6,261,693; 6,338,901;6,312,808; 6,280,834; 6,284,377; 6,335,086; 5,858,477; 5,635,245;5,888,593; 5,135,808; 5,900,342; and 5,470,661, all of which are herebyincorporated herein by reference.

It would sometimes be desirable to provide a window unit or other glassarticle with a protective coating including DLC in order to protect itfrom scratches and the like. Unfortunately, DLC tends to oxidize andburn off at temperatures of from approximately 380 to 400 degrees C. orhigher, as the heat treatment is typically conducted in an atmosphereincluding oxygen. Thus, it will be appreciated that DLC as a protectiveovercoat cannot withstand heat treatments (HT) at the extremely hightemperatures described above which are often required in the manufactureof vehicle windows, IG window units, glass table tops, and/or the like.Accordingly, DLC cannot be used alone as a coating to be heat treated,because it will oxidize during the heat treatment and substantiallydisappear as a result of the same (i.e., it will burn off).

Certain other types of scratch resistant materials also are not capableof withstanding heat treatment sufficient for tempering, heatstrengthening and/or bending of an underlying glass substrate.

Accordingly, those skilled in the art will appreciate that a need in theart exists for a method of making a scratch resistant coated articlethat is capable of being heat treated (HT) so that after heat treatmentthe coated article is still scratch resistant. A need for correspondingcoated articles, both heat treated and pre-HT, also exists.

BRIEF SUMMARY OF EXAMPLES OF INVENTION

In certain example embodiments of this invention, there is provided amethod of making a coated article (e.g., window unit such as for avehicle, building, or the like) that is capable of being heat treated sothat after being heat treated (HT) the coated article is scratchresistant to an extent more than uncoated glass.

In certain example embodiments of this invention, prior to heattreatment a coated article includes a layer of or including zirconiumnitride on a glass substrate. This may be the only layer on the glasssubstrate in certain example embodiments, or alternatively other layersmay be present. Heat treatment (e.g., thermal tempering) of the coatedarticle causes the zirconium nitride inclusive layer to transform eitherpartially or entirely into a layer of or including zirconium oxide thatcan be used for scratch resistant purposes.

In certain example instances, that are not limiting, the zirconium oxideinclusive layer following heat treatment may be buffed or surfacetreated in order to improve scratch resistance thereof. Moreover, thezirconium nitride inclusive layer, and thus the zirconium nitrideinclusive layer, may be doped with other materials such as F in certainexample non-limiting instances.

In certain example embodiments, an optional layer of diamond-like carbon(DLC) may be provided on the glass substrate over at least the zirconiumnitride inclusive layer prior to heat treatment. In certain exampleembodiments, the DLC may be hydrogenated. The DLC may be located belowand/or over the layer comprising zirconium nitride in certain exampleinstances. During HT, the hydrogenated DLC may act as a fuel which uponcombustion with oxygen produces carbon dioxide and/or water. Thisexothermic reaction, caused by combustion of hydrogenated carbon of theDLC, causes spontaneous propagation of a combustion wave through theinitial reactants. The high temperature developed during this combustionmay heat the layer comprising zirconium nitride to a temperature(s) wellabove the heat treating temperature, thereby causing the layercomprising zirconium nitride to be transformed into a new post-HT layercomprising zirconium oxide. The new post-HT layer comprising zirconiumoxide may also include nitrogen in certain example embodiments of thisinvention.

In certain example embodiments, at least prior to heat treatment, thelayer(s) comprising zirconium nitride may be doped with fluorine (F)and/or carbon (C). Surprisingly, it has been found that this tends toincrease the visible transmission of the heat treated coated article.

The new post-HT layer comprising zirconium oxide is surprisingly scratchresistant. Thus, it can be seen that a technique has been provided whichallows for a heat treatable scratch resistant product; and the coatedarticle may also have good transmission properties. In certain exampleembodiments, the scratch resistance of the post-HT coated article mayeven be better than that of non-HT DLC.

In certain example embodiments, there is provided a method of making aheat treated coated article, the method comprising: providing a coatingsupported by a glass substrate, the coating comprising a zirconiumnitride based layer; and thermally tempering the glass substrate withthe zirconium nitride based layer thereon, so that the tempering causesthe zirconium nitride based layer to transform into a layer comprisingzirconium oxide (Zr_(x)O_(y)) where y/x is from about 1.2 to 2.5. Alayer(s) comprising diamond-like carbon may optionally be provide overand/or under the layer comprising zirconium nitride in certain exampleembodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram illustrating coated articles according toan embodiment of this invention before and after heat treatment.

FIG. 2 is a schematic diagram illustrating coated articles according toanother embodiment of this invention before and after heat treatment.

FIG. 3 is an XPS graph illustrating chemical elements in a pre-HT coatedarticle according to an example of the instant invention.

FIG. 4 is an XPS graph illustrating chemical elements in the coatedarticle of FIG. 3, after the coated article of FIG. 3 has been subjectedto HT.

FIG. 5 is a schematic diagram illustrating coated articles according toan embodiment of this invention before and after heat treatment.

FIG. 6 is a schematic diagram illustrating coated articles according toanother embodiment of this invention before and after heat treatment.

FIG. 7 is a schematic diagram illustrating coated articles according toyet another embodiment of this invention before and after heattreatment.

FIG. 8 is a schematic diagram illustrating coated articles according toyet another embodiment of this invention before and after heattreatment.

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS OF THE INVENTION

Referring now more particularly to the accompanying drawings in whichlike reference numerals indicate like parts or layers throughout theseveral views.

In certain example embodiments of this invention, prior to heattreatment (HT) a coated article includes a layer of or includingzirconium nitride on a glass substrate. This may be the only layer onthe glass substrate in certain example embodiments, or alternativelyother layers may be present. Heat treatment (e.g., thermal tempering) ofthe coated article causes the zirconium nitride inclusive layer totransform either partially or entirely into a layer of or includingzirconium oxide that can be used for scratch resistant purposes.

Certain example embodiments of this invention relate to methods ofmaking coated articles that may use heat treatment (HT), wherein thecoated article includes a coating (one or more layers) includingdiamond-like carbon (DLC) and/or zirconium. In certain instances, the HTmay involve heating a supporting glass substrate, with the DLC and/orzirconium inclusive layer(s) thereon, to temperature(s) of from 550 to800 degrees C., more preferably from 580 to 800 degrees C. (which iswell above the burn-off temperature of DLC). In particular, certainexample embodiments of this invention relate to a technique for allowingthe post-HT coated article to be more scratch resistant than uncoatedglass.

In certain example embodiments, the coated article as originally formed(i.e., prior to HT, or pre-HT) includes respective alternating layerscomprising hydrogenated diamond-like carbon (DLC) and zirconium nitride,or possibly the coated article prior to HT may include only a layer ofor including zirconium nitride (which may be doped with othermaterial(s) as discussed herein). DLC may be located below and/or abovethe zirconium nitride. During HT (e.g., using temperature(s) of from 550to 800 degrees C., more preferably from 580 to 800 degrees C.), thehydrogenated DLC acts as a fuel which upon combustion with oxygen fromthe atmosphere produces carbon dioxide and water. This exothermicreaction, caused by combustion of the hydrogenated carbon of the DLC,causes spontaneous propagation of a combustion wave through the initialreactants. The high temperature developed during this DLC combustionheats the layer(s) comprising zirconium nitride to a temperature(s) wellabove the heat treating temperature used. For example, the combustion ofthe DLC may heat part of all of the layer(s) comprising zirconiumnitride to a temperature of at least about 1200 degrees C., morepreferably at least about 1500 degrees C., and most preferably at leastabout 2,000 degrees C. In embodiments where the DLC is not present priorto HT, the heat of the furnace during HT causes the zirconium nitride totransform into zirconium oxide during the HT.

Because the layer(s) comprising zirconium nitride is heated to such ahigh temperature due to the HT and/or DLC combustion during HT, at leastthe layer(s) comprising zirconium nitride is transformed due to the hightemperature(s) into a new post-HT layer(s) comprising zirconium oxide.The new post-HT layer(s) comprising zirconium oxide may also includenitrogen in certain example embodiments of this invention (e.g., ZrO:N;ZrO₂:N, ZrO_(x):N (where x is from 1 to 3, more preferably from 1.5 to2.5), and/or any other suitable stoichiometry). The new post-HT layer(s)comprising zirconium oxide (optionally with nitrogen) is surprisinglyscratch resistant. Thus, it can be seen that a technique has beenprovided which allows for a heat treatable scratch resistant product tobe made; and the coated article may also have good transmissionproperties. In certain example embodiments, the scratch resistance ofthe post-HT coated article may even be better than that of non-HT DLC.

In certain example embodiments of this invention, the post-HT layer(s)comprising zirconium oxide includes a nanocrystalline cubic latticestructure. The entire layer(s) may be of a nanocrystalline cubic latticestructure type, or alternatively only part of the layer(s) may includenanocrystalline cubic lattice structure. Zirconium nitride typicallydoes not grow in cubic phase unless at a temperature of at least about2,000 degrees C. The ZrN pre-HT is typically not in cubic lattice form.Since the HT is only at a temperature of no greater than about 900degrees C. (more preferably no greater than about 800 degrees C.), onewould expect that the pre-HT non-cubic zirconium nitride would not growin cubic phase during HT. However, it has surprisingly been found thatthe HT causes at least part of the layer comprising zirconium nitride tobe heated sufficiently to cause it to transform into a post-HT layer(s)comprising zirconium oxide which includes a nanocrystalline cubiclattice structure (with or without nitrogen) which is scratch resistant.

Thus, it can be seen that in certain example embodiments of thisinvention the pre-HT zirconium nitride inclusive layer is transformedduring HT into a new post-HT layer comprising zirconium oxide includinga nanocrystalline cubic lattice structure, even though the temperaturesused by the furnace during HT may be less than those required fortypically allowing the cubic growth.

As a result of the HT, the amount of oxygen in the post-HT zirconiuminclusive layer(s) is much higher than the amount of oxygen in thepre-HT zirconium inclusive layer(s). For example, in certain exampleembodiments of this invention, the post-HT layer(s) comprising zirconiumoxide includes at least 5 times as much oxygen as the pre-HT layer(s)comprising zirconium nitride, more preferably at least 10 times as much,and most preferably at least 20 times as much oxygen as the pre-HTlayer(s). In certain example embodiments of this invention, the pre-HTlayer(s) comprising zirconium nitride includes from about 0-10% oxygen,more preferably from about 0-5% oxygen, and most preferably from about0-2% (atomic %) oxygen. Meanwhile, in certain example embodiments ofthis invention, following HT and phase transformation due to DLCcombustion, the post-HT layer(s) comprising zirconium oxide includesmuch more oxygen as will be explained below.

In certain example embodiments, at least prior to heat treatment, one ormore of the layers comprising zirconium nitride may be doped withfluorine (F) and/or carbon (C). This may be done, for example, by usinga gas such as C₂F₆ during sputter-deposition of the layer(s) comprisingzirconium nitride. Surprisingly, it has been found that doping thezirconium nitride with F and/or C prior to heat treatment tends toincrease the visible transmission of the heat treated coated article. Ofcourse, following heat treatment the layer comprising zirconium oxidemay also be doped with F and/or C in a corresponding manner since it waspresent before HT. This doping of zirconium nitride (and/or zirconiumoxide) with F and/or C may be used in conjunction with any embodimentdiscussed herein.

FIG. 1 is a schematic diagram illustrating how a coated article can bemade according to an example embodiment of this invention. Initially, acoated article is formed using a glass substrate 1. The coated articleincludes, supported by glass substrate 1, at least one optionaldielectric layer 3 of or including silicon nitride, silicon oxynitride,silicon oxide, or the like; a first layer of or including DLC 5, a firstlayer of or including zirconium nitride 7 (e.g., ZrN, or any othersuitable stoichiometry), and a top layer of or including DLC 9. Glasssubstrate 1 is typically of or includes soda-lime-silica glass, althoughother types of glass may be used in certain instances.

Dielectric layer(s) 3 is provided in order to prevent sodium diffusioninto the DLC during HT (i.e., a diffusion barrier). This layer(s) 3 alsopermits thermal mismatching to occur without problems between the DLCand the glass substrate so as to more easily permit heat bending and thelike. Unexpectedly, it has been found that the use of silicon oxide as abarrier layer 3 (compared to silicon nitride) often leads to improvedoptical results of the final product after heat treatment such as highervisible transmission in certain example embodiments of this invention.Any of the aforesaid barrier layer 3 materials may be doped (e.g., 0.5to 15%) with Al, stainless steel, or any other metal(s) in certainembodiments of this invention. Barrier layer(s) 3 is formed on the glasssubstrate 1 via sputtering, or via any other suitable technique.

The layers 5 and 9 comprising DLC may be of any suitable type of DLC,including but not limited to any of the DLC types described in any ofU.S. Pat. Nos. 6,592,993; 6,592,992; 6,531,182; 6,461,731; 6,447,891;6,303,226; 6,303,225; 6,261,693; 6,338,901; 6,312,808; 6,280,834;6,284,377; 6,335,086; 5,858,477; 5,635,245; 5,888,593; 5,135,808;5,900,342; and/or 5,470,661, all of which are hereby incorporated hereinby reference.

For purposes of example only, DLC inclusive layer(s) 5 and/or 9 may eachbe from about 5 to 1,000 angstroms (Å) thick in certain exampleembodiments of this invention, more preferably from 10-300 Å thick, andmost preferably from 45 to 65 Å thick. In certain example embodiments ofthis invention, DLC layer(s) 5 and/or 9 may have an average hardness ofat least about 10 GPa, more preferably at least about 20 GPa, and mostpreferably from about 20-90 GPa. Such hardness renders layers 5 and 9resistant to scratching, certain solvents, and/or the like. Layer(s) 5and/or 9 may, in certain example embodiments, be of or include a specialtype of DLC known as highly tetrahedral amorphous carbon (t-aC), and maybe hydrogenated (t-aC:H) in certain embodiments. In certain hydrogenatedembodiments, the t-aC:H type of DLC may include from 4 to 39% hydrogen,more preferably from 5-30% H, and most preferably from 10-20% H.

This t-aC or t-aC:H type of DLC for layer(s) 5 and/or 9 may include moresp³ carbon-carbon (C—C) bonds than sp² carbon-carbon (C—C) bonds. Incertain example embodiments, at least about 50% of the carbon-carbonbonds in DLC layer(s) 5 and/or 9 may be sp³ type carbon-carbon (C—C)bonds, more preferably at least about 60% of the carbon-carbon bonds inthe layer(s) may be sp³ carbon-carbon (C—C) bonds, and most preferablyat least about 70% of the carbon-carbon bonds in the layer(s) may be sp³carbon-carbon (C—C) bonds. In certain example embodiments of thisinvention, the DLC in layer(s) 5 and/or 9 may have an average density ofat least about 2.4 gm/cm³, more preferably at least about 2.7 gm/cm³.

Example linear ion beam sources that may be used to deposit DLCinclusive layers 5 and 9 on substrate 1 include any of those in any ofU.S. Pat. Nos. 6,261,693, 6,002,208, 6,335,086, or 6,303,225 (allincorporated herein by reference). When using an ion beam source todeposit layer(s) 5 and/or 9, hydrocarbon feedstock gas(es) (e.g., C₂H₂),HMDSO, or any other suitable gas, may be used in the ion beam source inorder to cause the source to emit an ion beam toward substrate 1 forforming layer(s) 5 and/or 9. It is noted that the hardness and/ordensity of layer(s) 5 and/or 9 may be adjusted by varying the ion energyof the depositing apparatus. In certain example embodiments, at leastabout 2,000 V (anode to cathode volts), e.g., about 3,000 V, may be usedin the ion source in depositing layer(s) 5 and/or 9. It is noted thatthe phrase “on the substrate” as used herein is not limited to being indirect contact with the substrate as other layer(s) may still beprovided therebetween.

Zirconium nitride inclusive layer 7 is provided between DLC layers 5 and9 in certain example embodiments of this invention. In certain exampleembodiments, zirconium nitride inclusive layer 7 may be located directlybetween DLC layers 5 and 9 so as to contact each of them; however inother example embodiments other layer(s) (not shown) may be providedbetween the zirconium nitride inclusive layer 7 and the DLC layer(s) 5and/or 9. The zirconium nitride inclusive layer 7 may consistessentially of zirconium and nitride, or alternatively may include othermaterials including but not limited to oxygen, or other dopants such asAl, F, C or the like. Zirconium nitride inclusive layer 7 may be formedby sputtering or the like in certain example embodiments of thisinvention. The pre-HT layer(s) comprising zirconium nitride 7 (and 7′discussed below) may include from about 10-70% Zr, more preferably fromabout 30-65% Zr, even more preferably from about 40-60% Zr, and mostpreferably from about 45-55% Zr in terms of atomic %; and from about20-60% N, more preferably from about 30-50% N in terms of atomic %.

In certain example embodiments of this invention, zirconium nitrideinclusive layer 7 (and 7′ to be discussed below) may have a density ofat least 6 gm/cm³, more preferably at least 7 gm/cm³. Additionally, incertain example embodiments, zirconium nitride layer 7 (and 7′) may havean average hardness of at least 650 kgf/mm, more preferably of at least700 kgf/mm, and/or may have a bond overlap population of at least 0.25(more preferably at least about 0.30) for strength purposes. In certainexample instances, many of the Zr—N bonds in layer 7 (and 7′) may be ofthe covalent type, which are stronger than ionic bonds, for strengthpurposes. It is also noted that in certain example embodiments of thisinvention, the ZrN of layer 7 (and 7′) may have a melting point of atleast 2,500 degrees C., and it may be about 2,980 degrees C. in certainexample instances. In certain example embodiments of this invention, thezirconium nitride of layer 7 (and 7′) may be represented by Zr_(x)N_(y),where the ratio x:y is from 0.8 to 1.2, and is preferably about 1.0 incertain example embodiments.

For purposes of example only, certain example thicknesses for the pre-HTlayers shown on the left side of FIG. 1 are set forth below, with thelayers being listed in order from the glass substrate outwardly.

Example Coating (FIG. 1)—Layer Thicknesses (Pre-HT)

Layer General More Preferred Most Preferred Dielectric (layer 3) 50-500Å 100-300 Å  180-220 Å  DLC (layer 5) 10-300 Å 15-100 Å 20-45 Å ZrN(layer 7) 40-500 Å 50-400 Å 90-220 Å  DLC (layer 9) 20-300 Å 30-100 Å40-65 Å

Once the pre-HT coated article shown on the left side of FIG. 1 isformed, it may or may not be subjected to heat treatment sufficient forat least one of heat bending, thermal bending, and/or heatstrengthening.

Referring to FIG. 1, when subjected to HT (e.g., in a furnace usingtemperature(s) of from 550 to 800 degrees C., more preferably from 580to 800 degrees C.), the upper or outer DLC inclusive layer 9 burns offdue to combustion because of the high temperatures used during HT. Inparticular, at least hydrogenated DLC layer 9 acts as a fuel which uponcombustion with oxygen from the atmosphere during HT produces carbondioxide and water. This exothermic reaction, caused by combustion ofhydrogenated carbon from at least DLC layer 9, causes spontaneouspropagation of a combustion wave through the initial reactants. The hightemperature developed during this combustion heats the layer 7comprising zirconium nitride to a temperature(s) well above the heattreating temperature used by the furnace. For example, the combustion ofthe DLC 9 may heat part of all of the layer 7 comprising zirconiumnitride to a temperature of at least about 1200 degrees C., morepreferably at least about 1500 degrees C., and most preferably at leastabout 2,000 degrees C.

Because the layer comprising zirconium nitride 7 is heated to such ahigh temperature due to the DLC combustion during HT, the layercomprising zirconium nitride 7 is transformed during the HT into a newpost-HT layer comprising zirconium oxide 11. The new post-HT layercomprising zirconium oxide 11 may also include nitrogen (and/or otherdopants) in certain example embodiments of this invention (e.g., ZrO:N;ZrO₂:N; or any other suitable stoichiometry). The new post-HT layercomprising zirconium oxide 11 (optionally with nitrogen) is surprisinglyscratch resistant thereby providing a heat treated scratch resistantcoated article. It is noted that the phrase “zirconium oxide” as usedherein includes ZrO₂ and/or any other stoichiometry where Zr is at leastpartially oxided. Herein, any description of layer 11 also may apply tolayer 11′; and likewise any description of layer 7 may apply to layer7′.

The post-HT layer comprising zirconium oxide 11 may include from 0-30%nitrogen in certain example embodiments of this invention, morepreferably from 0-20% nitrogen, even more preferably from 0-10%nitrogen, and most preferably from about 1-5% nitrogen in certainexample embodiments of this invention. The post-HT layer comprisingzirconium oxide 11 may include from about 10-70% Zr, more preferablyfrom about 20-60% Zr, even more preferably from about 30-55% Zr, andmost preferably from about 30-45% Zr in terms of atomic %. Moreover, thepost-HT layer(s) comprising zirconium oxide 11 in certain exampleembodiments of this invention may include from about 10-85% oxygen, morepreferably from about 30-80% oxygen, even more preferably from about40-70% oxygen, and most preferably from about 50 to 70% oxygen.

In certain example embodiments of this invention, the post-HT layercomprising zirconium oxide 11 includes a nanocrystalline cubic latticestructure (although the pre-HT layer comprising zirconium nitride didnot in certain instances). As explained above, zirconium nitridetypically does not grow in cubic phase unless at a temperature of atleast about 2,000 degrees C. It has surprisingly been found that thecombustion generated by the DLC during HT causes at least part of thepre-HT layer comprising zirconium nitride 7 to be heated sufficiently tocause it to grow in the cubic phase and become a post-HT layer 11comprising a nanocrystalline cubic lattice structure including zirconiumoxide (with or without nitrogen) which is very scratch resistant incertain example embodiments of this invention.

It has surprisingly been found that the use of zirconium nitride (e.g.,ZrN) in the pre-HT layer 7 is especially beneficial with respect toallowing a post-HT phase-transformed layer 11 including Zr to be formedwhich is very scratch resistant.

The final HT (or even the non-HT) coated article of FIG. 1 is scratchresistant and may be used in various applications, including but notlimited to IG window units, laminated vehicle windshields, other typesof vehicle windows, furniture applications, and/or the like.

For purposes of example only, certain example thicknesses for thepost-HT coated article shown on the right side of FIG. 1 are set forthbelow, with the layers being listed in order from the glass substrateoutwardly.

Example Coating (FIG. 1)—Layer Thicknesses (Post-HT)

Layer General More Preferred Most Preferred Dielectric (layer 3) 50-500Å 100-300 Å  180-220 Å DLC (layer 5)  0-300 Å 15-100 Å  20-45 Å ZrO:N(layer 11) 50-800 Å 70-600 Å 100-350 Å

It can be seen from the above that post-HT Zr inclusive layer 11 istypically thicker than is pre-HT Zr inclusive layer 7. In other words,the thickness of the Zr inclusive layer increases during Hf. In certainexample embodiments of this invention, the thickness of the Zr inclusivelayer (e.g., from layer 7 to layer 11) may increase at least about 5%during or due to HT, more preferably at least about 10%, and mostpreferably at least about 40%. This increase in thickness is caused bythe transformation of layer 7 into layer 11, where oxygen migrates intothe post-HT layer 11 (i.e., more oxygen migrates into the post-HT layer11 than nitrogen leaves in terms of atomic % and/or size).

While the DLC layer 5 is shown as being present in the post-HT coatedarticle in FIG. 1, it need not be present in the post-HT coated articlein alternative embodiments of this invention. If the pre-HT DLC layer 5reaches sufficient temperature and/or is exposed to enough oxygen duringHT, it may be subject to combustion thereby causing it to decrease inthickness or even vanish due to HT in certain instances. In such cases,the pre-HT layers 5, 7 and/or 9 may be effectively transformed during HTinto post-ITF zirconium oxide inclusive layer 11 (it is similar to theFIG. 5 embodiment in this regard).

In certain example embodiments of this invention, the heat treated layer11 comprising zirconium oxide includes Zr_(x)O_(y), wherein y/x is fromabout 1.2 to 2.5, more preferably from about 1.4 to 2.1.

FIG. 2 illustrates another example embodiment according to thisinvention. The FIG. 2 embodiment is similar to the FIG. 1 embodiment,except that additional ZrN inclusive layer(s) 7′ and additional DLCinclusive layer(s) 5′ are provided pre-ITf. In other words, the FIG. 2embodiment includes plural sets of alternating layers comprising DLC andZrN pre-HT. Thus, following HT, an additional zirconium oxide inclusivelayer(s) 11′ and an additional DLC inclusive layer 5′ may be provided asshown on the right side of FIG. 2. Layers 5′, 7′, and 11′ are similar tolayers 5, 7, and 11, respectively, discussed above, in certain exampleembodiments of this invention. However, it is possible that one or bothof hydrogenated DLC layers 5, 5′ may be subject to combustion andsubstantially disappear or substantially decrease in thickness due to HTin certain example embodiments of this invention when high temperatureand/or long heating times are used so that a single ZrO layer remains(e.g., see FIG. 5), although some DLC may remain as shown in FIG. 2.However, as shown in the FIG. 2 embodiment, at least the outerhydrogenated DLC layer 9 typically burns off due to combustion andgenerates the energy/heat needed to cause one of more of the ZrNlayer(s) 7, 7′ to transform into ZrO inclusive layer(s) 11, 11′ asexplained above.

Still referring to the FIG. 2 embodiment, in certain examplenon-limiting embodiments of this invention, oxygen from the atmospherediffuses inwardly through the layers(s) in order to help the pre-HTzirconium nitride layers 7 and 7′ to transform, aided by the heatgenerated by the combustion discussed above, into the post-HT layers 11and 11′ comprising zirconium oxide. However, in other exampleembodiments of this invention, pre-HT zirconium nitride layer 7′ neednot phase transform during HT; in such embodiments, the post-HT layer11′ would be similar to the pre-HT layer 7′ and consist essentially ofzirconium nitride. In still other embodiments of this invention, layer11′ may be partially transformed and thus include a mixture of zirconiumnitride and zirconium oxide.

FIGS. 3-5 illustrate another example embodiment of this invention. Thepre-HT coated article of this embodiment is the same as that of the FIG.2 embodiment described above. FIG. 3 is an XPS graph illustrating thechemical make-up of an example coated article pre-HT according to theFIG. 5 embodiment. However, in contrast to the FIG. 2 illustratedembodiment, in the FIG. 5 embodiment during HT all DLC layers aresubject to combustion and essentially disappear. This in turn creates asignificant amount of heat and coupled with oxygen diffusing into thecoating from the surrounding atmosphere causes each of the pre-HTzirconium nitride layers to phase transform during HT so as to form atleast one post-HT layer comprising zirconium oxide (which may or may notbe doped with N) 11. In the FIG. 5 embodiment, the pre-HT layers 5, 7′,5′, 7 and 9 merge into or ultimately result in one rather thick post-HTlayer comprising zirconium oxide 11. FIG. 4 is an XPS graph illustratingthe chemical make-up of an example post-HT coated article according tothe FIG. 5 embodiment.

In the FIGS. 3-5 embodiment, it can be seen in FIG. 4 that residualcarbon remains in the zirconium oxide layer 11 following HT due to thepresence of the pre-HT DLC layer(s). In certain example embodiments ofthis invention, the zirconium oxide layer 11 includes from 0.25 to 20%C, more preferably from 0.25 to 10% C, and most preferably from 0.25 to5% C.

FIG. 6 is a cross sectional view of another example embodiment of thisinvention. In the FIG. 6 embodiment, the optional layer 5 comprising DLCis located directly on the glass substrate 1. Certain carbon atoms maybe subimplanted into the substrate in certain example instances toimprove bonding. Zirconium nitride inclusive layer 7 is located betweenand contacting DLC layers 5 and 9 in this example embodiment. As withthe other embodiments discussed herein, the zirconium nitride may bedoped with F and/or C in certain example embodiments of this invention.During heat treatment, at least outer DLC inclusive layer 9 acts as afuel to cause at least layer 7 to transform into a new post-HT layer 11comprising or consisting essentially of zirconium oxide as shown in FIG.6 and described above. DLC layer 5, during HT, may act as a fuel and/ormay melt into the glass and/or layer 7, 11 during HT as a result ofcombustion.

When layer 5 melts into the glass 1 during HT, the result is atransitional interface layer proximate the substrate surface thatcomprises silicon oxycarbide. In certain embodiments of this invention,DLC layer 5 may function as a Na barrier to prevent significant amountsof Na from migrating from the glass to the zirconium inclusive layerduring HT, so as to reduce the likelihood of damage to the Zr inclusivelayer.

In certain other instances, it is possible that the DLC layer 5 mayshrink but not entirely disappear during ITF in certain exampleembodiments of this invention.

In the FIG. 6 embodiment, DLC layer 5 may be from about 20 to 60 Åthick, more preferably from 28 to 34 Å thick, or may be any othersuitable thickness; ZrN inclusive layer 7 may be from about 100 to 200 Åthick, more preferably from about 150 to 190 Å thick, most preferablyfrom about 160 to 170 Å thick, or may be any other suitable thickness;and DLC layer 9 may be from 50 to 200 Å thick, more preferably from 80to 120 Å thick, most preferably from 90 to 110 Å thick, or any othersuitable thickness in certain example instances. In certain instances,if the thickness of the bottom DLC layer 5 falls outside of the range 28to 34 Å, undesirable haze can increase rapidly, especially on the lowside.

FIG. 7 is a cross sectional view of another example embodiment of thisinvention. The FIG. 7 embodiment is similar to the FIG. 6 embodiment,except for the omission of bottom DLC layer 5. Thus, in the FIG. 7embodiment, the layer 7 comprising zirconium nitride is located directlyon the glass substrate 1 before HT. As with the other embodimentsdiscussed herein, the zirconium nitride 7 may be doped with F and/or Cin certain example embodiments of this invention, and thus the heattreated zirconium oxide 11 may be doped with F and/or C in a similarmanner. In the FIG. 7 embodiment, for example, layer 7 may be from about50-400 Å thick, more preferably from about 80-200 Å thick, and mostpreferably from about 120-180 Å thick; and DLC layer 9 may be from about30 to 400 Å thick, more preferably from about 50 to 150 Å thick, andmost preferably from about 80 to 120 Å thick.

As an alternative of the FIG. 7 embodiment, an underlayer (not shown inFIG. 7) may be provided between the zirconium nitride layer 7 and thesubstrate 1. This underlayer may be of, or include, a material such assilicon oxide (e.g., SiO₂) or silicon nitride. This underlayer issimilar to dielectric layer 3 shown in FIGS. 1, 2 and 5 for example.

FIG. 8 is a cross sectional view of another example embodiment of thisinvention. The FIG. 8 embodiment is similar to the FIG. 6 and FIG. 7embodiments, except for the omission of the DLC layers 5, 9. Thus, inthe FIG. 8 embodiment, the layer 7 comprising zirconium nitride may belocated directly on the glass substrate 1 before HT. As with the otherembodiments discussed herein, the zirconium nitride 7 may be doped withF and/or C in certain example embodiments of this invention, and thusthe heat treated zirconium oxide 11 may be doped with F and/or C in asimilar manner. In the FIG. 8 embodiment, it has been found that it hasbeen surprisingly helpful to make the zirconium nitride inclusive layer7 somewhat thicker. In particular, in the FIG. 8 embodiment for examplelayer 7 may be from about 150-400 Å thick, more preferably from about200-320 Å thick. If the layer 7 is thicker than this, then visibletransmission may suffer, whereas if the thickness is lower than thisthen stain resistance (i.e., resistance to corrosion of the coatedarticle) may suffer following HT. Zirconium nitride inclusive layer 7may be deposited on substrate 1 by sputtering a Zr or Zr inclusivetarget in certain example embodiments of this invention.

The FIG. 8 embodiment has been found to be advantageous in that a widerprocess window for tempering may be possible since samples that havebeen over-cooked during HT have not shown streaks or haze in contrastwith DLC inclusive embodiments discussed herein. Thus, the FIG. 8embodiment may ease tolerance requirements in the manufacturing process.Moreover, in the FIG. 8 embodiment, it has been found that surfacetreatment (e.g., mechanical buffing) improves the scratch resistance ofpost-HT zirconium oxide based layer 11.

As an alternative of the FIG. 8 embodiment, an underlayer (not shown inFIG. 8) may be provided between the zirconium nitride layer 7 and thesubstrate 1. This underlayer may be of, or include, a material such assilicon oxide (e.g., SiO₂) or silicon nitride. This underlayer issimilar to dielectric layer 3 shown in FIGS. 1, 2 and 5 for example.

In any of the example embodiments discussed above, one or more of thelayers comprising zirconium nitride (7 and/or 7′) may be doped withfluorine (F) and/or carbon (C). This may be done, for example, by usinga gas such as C₂F₆ during sputter-deposition of the layer(s) comprisingzirconium nitride. For instance, a layer of ZrN:F (7 and/or 7′) may beformed by sputtering a Zr inclusive target(s) in an atmosphere includinga mixture of N₂ and C₂F₆ gases (Ar gas may also be used in certainexample instances in addition to N₂ and C₂F₆ gases). When C₂F₆ gas isused in the sputtering atmosphere, the resulting layer comprising ZrN istypically doped with both F and C since both are present in the gas.Other gases could instead be used.

Surprisingly, it has been found that doping the zirconium nitride (7and/or 7′) with F and/or C prior to heat treatment tends to increase thevisible transmission of the heat treated coated article. Doping with Fand C unexpectedly results in a film with lower absorption compared toundoped films. Moreover, it has been found that the addition of F and/orC to these layers does not significantly change the optics of the coatedarticle, or the biaxial film stress of the films prior to HT.Furthermore, when F and/or C are provided in layer 7 and/or 7′, bothscratch resistance and environmental stability (e.g., measured via saltfog test) of the HT product are substantially unaffected by the presenceof F and/or C. Of course, following heat treatment the layer comprisingzirconium oxide (11 and/or 11′) may also be doped with F and/or C in acorresponding manner since it was present before HT. This doping ofzirconium nitride (and/or zirconium oxide) with F and/or C may be usedin conjunction with any embodiment discussed herein.

In certain example embodiments of this invention, one or more of layers7, 7′, 11 and 11′ may be doped with from about 0.01 to 10.0% F, morepreferably from about 0.1 to 8.0% F, even more preferably from about 0.3to 5.0% F, still more preferably from about 0.4 to 2% F, and mostpreferably from about 0.5 to 1.0% F (in terms of atomic percent).Moreover, in certain example embodiments of this invention, one or moreof layers 7, 7′, 11 and 11′ may be doped with from about 0.01 to 10.0%C, more preferably from about 0.1 to 8.0% C, even more preferably fromabout 0.3 to 5.0% C, still more preferably from about 0.4 to 2% C, andmost preferably from about 0.5 to 1.0% C (in terms of atomic percent).The doping with F and C may be used together so that one or more oflayers 7, 7′, 11 and 11′ is/are doped with both F and C in theseamounts. Alternatively, only one of the dopants F and C may be used fora layer. Thus, in such alternative embodiments, one or more of layers 7,7′, 11 and 11′ may be doped with F in the aforesaid amount(s), but notdoped with C. As yet another alternative, one or more of layers 7, 7′,11 and 11′ may be doped with C in the aforesaid amount(s), but not dopedwith F.

Each of the aforesaid embodiments provides for a heat treatable coatedarticle that is very scratch resistant following HT. For example,post-HT coated articles according to certain embodiments of thisinvention may have a critical scratch load using an alumina sphere of atleast about 15 lbs., more preferably at least 18 lbs., even morepreferably at least 20 lbs., still most preferably at least 22.5 lbs.,and most preferably at least 30 lbs. Additionally, coated articlesaccording to certain example embodiments of this invention are UVstable, and do not significantly degrade upon UV exposure. In certainexample embodiments, coated articles herein may have a post-HT contactangle θ with a sessile drop of water of from about 25 to 60 degrees; andsometimes the contact angle is less than 35 degrees.

Moreover, in certain example embodiments, good optics are provided inthat no significant yellow tint is present post-HT even though yellowishDLC may have been present at least in the pre-HT version of the product.The resulting heat treated coated article is surprisingly transmissiveto visible light. For example, the heat treated coated article may havea visible transmission of at least 50%, more preferably of at least 60%,even more preferably of at least 70%, more preferably at least 75%, andsometimes at least 80% according to certain example embodiments of thisinvention. According to certain example embodiments of this invention,post-HT coated articles have a transmissive a* value of from −5 to +2,more preferably from −4 to 0, and most preferably from −3.5 to −1; and atransmissive b* value of from −8 to +8, more preferably from −3 to +1,and most preferably from −2 to +2. In other words, heat treated coatedarticles according to certain example embodiments of this inventionvisually appear very similar to clear uncoated glass, even though thenumerous layers for durability purposes are provided thereon.

Another unique aspect of certain example embodiments of this inventionis the extreme increase in visible transmission caused by heattreatment. In certain example embodiments, visible transmissionincreases by at least about 20 visible transmission % due to HT, morepreferably at least 30%, and most preferably at least 40%. For example,in certain examples of this invention that have been made, the pre-HTvisible transmission has been about 36-37%. Following heat treatment forabout 400 seconds at about 640 degrees C., the post-HT visibletransmission was about 77-81%. In each case, the visible transmissionincreased by about 40-45% due to HT. For purposes of example andunderstanding, if a pre-HT coated article had a visible transmission of36% and following HT the post-HT coated article had a visibletransmission of 80%, then the visible transmission increased 44% (i.e.,80%-36%=44%) due to HT. The apparent reason for this significantincrease in visible transmission due to HT is the vanishing of at leastsome DLC due to HT because of the aforesaid combustion thereof. DLCblocks visible transmission to some extent, and its combustion anddisappearance during HT allows visible transmission of the resulting HTcoated article to significantly increase as shown above. Thus, not onlydoes the DLC combustion act as a fuel which allows transformation of theZr inclusive layer, but it also allows visible transmission tosignificantly increase.

Any suitable type of glass substrate 1 may be used in differentembodiments of this invention. For example, various types of soda limesilica glass or borosilicate glass may be used for substrate 1. However,in certain example embodiments of this invention, the coating of any ofthe aforesaid embodiments may be supported by a special type of glasssubstrate that has a very high visible transmission and a very clearcolor. In particular, in such certain example embodiments of thisinvention, the glass substrate 1 may be any of the glasses described incommonly owned U.S. patent application Ser. No. 10/667,975, thedisclosure of which is hereby incorporated herein by reference. Incertain preferred embodiments, the resulting glass has visibletransmission of at least 85%, more preferably at least 88%, and mostpreferably at least 90% (e.g., at a reference thickness of about 0.219inches or 5.56 mm). The advantage of using such a glass substrate 1 isthat the resulting HT product is caused to have a visual appearancesimilar to that of uncoated clear glass—even though the coating isprovided thereon. In addition to the base glass, examples of the glassbatch and/or final glass are set forth below (in terms of weightpercentage of the total glass composition, unless otherwise listed asppm):

Example Colorants and Oxidizer Cerium in Glass Substrate

Ingredient General Preferred More Preferred Best total iron (Fe₂O₃):0.01-0.20% 0.01-0.15% 0.02-0.12% 0.03 to 0.10% cobalt oxide: 0 to 15 ppm0.1 to 10 ppm 0.5 to 5 ppm 0.5 to 3 ppm cerium oxide: 0.005-1.0%0.01-1.0% 0.01-0.5% 0.05 to 0.2% erbium oxide: 0 to 1.0% 0.01-0.30%0.02-0.20% 0.02 to 0.15% titanium oxide: 0 to 0.5% 0 to 0.2% 0.001 to0.05% 0.01 to 0.02% chromium oxide: 0 to 10 ppm 0 to 8 ppm 0 to 5 ppm 1to 5 ppm glass redox: <=0.20 <=0.12 <=0.10 <=0.08 % FeO: 0.0001-0.05%0.0001-0.01% 0.001-0.008% 0.001-0.003%

It is noted that in other embodiments of this invention, additionallayers (not shown) may be added to the coated articles discussed above,and/or certain layer(s) may be deleted.

EXAMPLE 1

For purposes of example, and without limitation, the following examplecoated article was made and tested according to an example embodiment ofthis invention. This Example 1 is similar to the FIG. 5 embodiment.

The glass substrate 1 was cleaned/washed. It was then ion beam etchedusing argon gas to clean the surface thereof. Then, a silicon nitridebarrier layer 3 (doped with Al) about 100 Å thick, a DLC (ta-C:H type)layer 5 about 70 Å thick, a zirconium nitride layer 7′ about 100 Åthick, another DLC (ta-C:H type) layer 5′ about 70 Å thick, anotherzirconium nitride layer 7 about 100 Å thick, and a sacrificial outer DLC(ta-C:H type) layer 9 about 70 Å thick were formed on a glass substrate(see FIG. 5). The ZrN layers 7 and 7′ were formed via sputtering a Zrtarget in an atmosphere including N and Ar, and the DLC layers wereformed via ion-beam deposition using an anode-cathode voltage of about3,000 V and acetylene feedstock gas.

FIG. 3 is an XPS graph illustrating the pre-HT chemical make-up of thecoated article according to this Example. As can be seen in FIG. 3, thecarbon (C) spikes indicate the DLC layers 5 and 5′, whereas the Zrspikes indicate the ZrN layers 7 and 7′. It is noted that the C contentincreases on the left edge of the FIG. 3 graph showing the thin DLCsacrificial layer 9 at the outermost layer of the pre-HT coating. Thehigh oxygen content on the right side of the graph indicates the glasssubstrate, and the combination of the Si and N spikes in the same areaindicates the optional silicon nitride barrier layer 3.

The coated article of Example 1 was then subjected to HT at about 625degrees C. for about four minutes.

FIG. 4 is an XPS graph of the coated article of FIG. 3 (i.e., of thisExample 1) after the HT. FIG. 4 illustrates that the overcoat DLC layer9 burned off during HT due to combustion, and that pre-HT layers 5, 7′,5′ and 7 merged or were transformed into a thick layer consistingessentially of scratch resistant zirconium oxide 11 that was slightlydoped with nitrogen (see the right-hand coated article in FIG. 5 whichis the post-HT article). It can be seen in FIG. 4 that residual carbonis left over in the zirconium oxide layer 11 due to the previous DLClayers which were present prior to heat treatment.

EXAMPLE 2

Example 2 was made in accordance with the FIG. 6 embodiment. On a 10 mmthick clear glass substrate having a composition similar to thatdiscussed above, layers 5, 7 and 9 were formed as shown in FIG. 6. DLClayer 5 was 34 Å thick, ZrN layer 7 was 160 Å thick, and DLC layer 9 was100 Å thick. The two DLC layers were formed via ion beam depositionusing acetylene gas, while the zirconium nitride layer 7 was formed viasputtering using a power of about 3 kW. Following heat treatment, thecoated article included substrate 1 and zirconium oxide layer 11 thatincluded some nitrogen as shown on the right side of FIG. 6.

Following HT, based on three different samples of this example, thecoated article of this example on average had a visible transmission ofabout 78.61%, a critical scratch load (CSL) of 31 lbs. and a haze valueof 1.6.

EXAMPLE 3

Example 3 was made in accordance with the FIG. 7 embodiment. On a 10 mmthick clear glass substrate 1 having a composition similar to thatdiscussed above, layers 7 and 9 were formed as shown in FIG. 7. ZrNlayer 7 was 160 Å thick, and DLC layer 9 was from 60-100 Å thick. Aswith other examples, the zirconium nitride layer was formed bysputtering. Following heat treatment, the coated article includedsubstrate 1 and zirconium oxide layer 11 that included some nitrogen asshown on the right side of FIG. 7.

Following HT, based on three different samples of this example, thecoated article of this example on average had a visible transmission ofabout 81.35%, a critical scratch load (CSL) of 10.8 lbs. and a hazevalue of 0.44.

In certain example non-limiting embodiments of this invention, coatedarticles following HT may have a visible transmission of at least 70%,more preferably of at least 75%. In certain example non-limitingembodiments of this invention, coated articles following HT may have ahaze value of no greater than 2.5, more preferably no greater than 1.75,and sometimes no greater than 1.0.

EXAMPLE 4

In Example 4, a coated article was made in accordance with the FIG. 8embodiment. A ZrN layer 7 was sputter deposited directly on a glasssubstrate using a Zr target in an atmosphere including Ar and N gases,to a thickness of about 326 angstroms. The Ar gas flow per cathode was190 sccm, the N₂ gas flow per cathode was 79.2 sccm, the operatingpressure in the sputtering chamber was 2.4 mTorr, and the N₂/power ratiowas about 6.1. The glass substrate was clear glass about 6 mm thick. Ascoated, prior to heat treatment, the coated article had a visibletransmission of about 38%. The coated article was then heat treated in abox oven furnace for about 4-5 minutes, and following heat treatmentmechanical buffing using greater than 10 lbs of pressure was performedon the outer surface of the zirconium oxide based layer 11. The heattreatment caused the zirconium nitride based layer 7 to transform into azirconium oxide based layer 11. Following the heat treatment, the coatedarticle had a visible transmission of about 79%. There were no signs ofstreaks of haze following the heat treatment, and scratch resistance wasgood.

With respect to any embodiment herein, the glass substrate may be ionbeam milled prior to deposition of a coating thereon. For example, astep of ion beam milling the glass substrate 1 (e.g., the non-tinsurface thereof) may be performed so as to remove at least 2 Å (morepreferably at least 5 Å, and most preferably at least 10 Å) of glassfrom at least a portion (and possibly the entire) glass substratesurface. Then, after the ion beam milling of the glass substrate 1, thebase layers 3, 5 and/or 7 and then the other layers are deposited on theion beam milled surface of the glass substrate 1. For example, glasssubstrate 1 may be ion beam milled using any technique for ion beammilling described in U.S. Pat. Nos. 6,777,030 and/or 6,740,211, thedisclosures of which are hereby incorporated herein by reference.

While the invention has been described in connection with what ispresently considered to be the most practical and preferred embodiments,it is to be understood that the invention is not to be limited to thedisclosed embodiments, but on the contrary, is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims.

1. A method of making a heat treated coated article, the methodcomprising: providing a coating supported by a glass substrate, thecoating comprising a zirconium nitride based layer; and thermallytempering the glass substrate with the zirconium nitride based layerthereon, so that the tempering causes the zirconium nitride based layerto transform into a layer comprising zirconium oxide (Zr_(x)O_(y)) wherey/x is from about 1.2 to 2.5.
 2. The method of claim 1, wherein y/x isfrom about 1.4 to 2.1.
 3. The method of claim 1, wherein the zirconiumnitride based layer further comprises fluorine and/or carbon.
 4. Themethod of claim 1, wherein the layer comprising zirconium oxide furthercomprises fluorine and/or carbon.
 5. The method of claim 1, whereinprior to the tempering, the coating further comprises a layer comprisingdiamond-like carbon located between the glass substrate and thezirconium nitride based layer.
 6. The method of claim 1, wherein priorto the tempering, the coating further comprises a layer comprisingdiamond-like carbon located on the glass substrate over at least thezirconium nitride based layer.
 7. The method of claim 1, wherein priorto and/or after the tempering, the coating further comprises adielectric layer between the glass substrate and the zirconium nitridebased layer.
 8. The method of claim 1, wherein the layer comprisingzirconium oxide comprises a nanocrystalline cubic lattice structure. 9.The method of claim 1, wherein the layer comprising zirconium oxidecomprises from about 30-80% oxygen.
 10. The method of claim 1, whereinthe layer comprising zirconium oxide comprises from about 50 to 70%oxygen.
 11. The method of claim 1, wherein the layer comprisingzirconium oxide comprises from about 20-60% Zr.
 12. The method of claim1, wherein the layer comprising zirconium oxide comprises from about30-55% Zr.
 13. The method of claim 1, wherein the layer comprisingzirconium oxide comprises from about 30-45% Zr and from about 0-10% N.14. The method of claim 1, wherein the layer comprising zirconium oxideis an outermost layer of the coated article following heat treatment.15. The method of claim 1, wherein visible transmission % of the coatedarticle increases by at least 30% due to the tempering.
 16. The methodof claim 1, wherein the tempered coated article has a transmissive a*value of from −4 to 0, and a transmissive b* value of from −3 to +3. 17.The method of claim 1, wherein the tempered coated article has a visibletransmission of at least 70%.
 18. The method of claim 1, wherein thecoated article after tempering has a visible transmission of at least70% and a critical scratch load using an alumina sphere of at leastabout 20 lbs.
 19. A method of making a heat treated coated article, themethod comprising: providing a coating supported by a glass substrate,the coating comprising a layer comprising zirconium nitride; andthermally tempering the glass substrate with the layer comprisingzirconium nitride, so that the tempering causes zirconium nitride totransform into a layer comprising zirconium oxide (Zr_(x)O_(y)) wherey/x is from about 1.2 to 2.5.